Effects of Intermolecular Hydrogen-bonding on the Luminescence Properties of Acetophenone, Characterization of Emission States

Abstract The effects of intermolecular hydrogen-bond formation by protic solvents on the absorption and luminescence properties of acetophenone have been investigated. It has been concluded from analysis of the T←S0 absorption, phosphorescence excitation spectra and the emission characteristics that the lowest triplet state of acetophenone in its vapor phase and in nonpolar as well as in moderately polar solvents (e.g., ethanol, EPA etc.) is of n-π* character. In rigid polar media, acetophenone exhibits a very weak 1π-π*→S0 fluorescence and a weak 3π-π*→S0 phosphorescence superposed with the principal 3π-π*→S0 emission. A progressive enhancement of both of these emissions with increasing polarity of the solvent has been observed. It is shown that the fluorescence and the dual phosphorescence emissions from acetophenone in rigid polar media arise as a result of decreased efficiencies of the spin-orbit and vibronic coupling interactions due to intermolecular hydrogen-bond formation by the protic solvents.